Adhesive transparent resin and a composite including the same

ABSTRACT

To provide a transparent resin which is suitable in the process of producing a coating for electronic materials, a glass having both of the scattering-preventing function and the antireflective function, an adhesive agent, a shock-absorbing material, an ultraviolet-cutting sheet for televisions, a filter for VDTs and a high refractive index primer composition as well as the process for the production of primer-coated lenses using the primer composition, is excellent in a coatability, adhesive property, storage stability, durability, shock resistance and the like, and is particularly excellent in a transparency and adhesive property after curing of the same. A transparent resin having an adhesive property characterized by comprising a cured product of the polymerizing composition which comprises at least one of diallyl phthalate, diallyl isophthalate and diallyl terephthalate, and pentaerydiritol tetra(3-mercaptopropionate).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 08/910,215, filedAug. 13, 1997, now U.S. Pat. No. 6,224,976, and claims priority ofJapanese Application Nos. 8-214748 filed Aug. 14, 1996, 8-214749 filedAug. 14, 1996, 8-214753 filed Aug. 14, 1996, 8-214754 filed Aug. 14,1996, 8-214756 filed Aug. 14, 1996, 9-68283 filed Mar. 21, 1997,9-106405 filed Apr. 23, 1997, 9-119149 filed May 9, 1997, 9-144020 filedJun. 2, 1997, 9-144021 filed Jun. 2, 1997, 9-174403 filed Jun. 30, 1997,and 9-174404 filed Jun. 30, 1997. The entire disclosure of applicationSer. No. 08/910,215 is considered as being part of the disclosure ofthis application, and the entire disclosure of application Ser. No.08/910,215 is expressly incorporated by reference herein in itsentirety.

FIELD OF THE INVENTION

The present invention relates to;

an ultraviolet (UV)-curable composition for forming a coating ofelectronic materials, such as a surface protective layer ofsemiconductors, an insulating layer of semiconductor-mounted devices, asurface protective coating of color filters in liquid crystal displaydevices, an insulating interlayer of multilayered printed circuits and aprotective coating of light guiding materials or phase shiftingmaterials,

a glass having both of the scattering-preventing properties and theanti-reflective properties, which is useful for display devices,construction materials, lenses, automobile parts, furniture and others;

an adhesive agent which shows only a little aging under a hightemperature and high humidity conditions, and shows an excellentadhesion property with optical films,

a shock-absorbing material, such as plate glass, glass articles,potteries and others, which can protect fragile articles liable to bedamaged during transportation or storage,

an easily removable ultraviolet (UV)-cutting sheet fixed onto a surfaceof glass, which is exposed to sunlight in various architecturalstructures, such as housing, buildings, traffic systems, vendingmachines, oceanic constructions,

a easily removable UV-screening filter fixed onto a display surface oftelevisions,

a filter for a shield for electromagnetic waves, and for shielding UVrays and preventing electrostatic charging in VDTs (visual displayterminals) such as personal computers, word processors and otherdevices, and

a transparent resin having a nigh adhesion property capable ofconstituting a high refractive index primer composition for plasticlenses.

PRIOR ART

Recently, a variety of color liquid crystal display devices comprising acombination of a liquid crystal device and a color filter for colorseparation have become widely used. The color filter is generallyconstituted by a glass substrate, picture elements formed on thesubstrate, a layer of protective coating, and a transparent electrode ofindium-tin oxide (ITO), in this order from the substrate. For the layerof protective coating, it is necessary to satisfy a wide range orproperties such as;

an adhesion property to picture elements, grass, chromium used as ablack matrix component, which constitute a lower layer of the device,

an adhesion property to ITO constituting an upper layer,

an adhesion property to an epoxy sealing agent constituting a liquidcrystal cell,

capabilities of shielding impurities of the picture elements, ofsmoothness, of wet heat resistance, of light fastness, of resistance tosolvents, of chemical resistance, of dampness, of transparency,

a capability of heat resistance required in the posterior-processing inthe production of liquid crystal cells, and the like.

Further, similar properties are required for a protective coating of theglass substrate. For materials for forming the protective coating, aheat curable composition, such as siloxane polymer, silicone polyimideand the like, has been particularly suggested in view of the heatresistance of the heat curable composition. The examples using thesiloxane polymer are well-known from Japanese Unexamined PatentPublication (Kokai) Nos. 63-241076, 3-126612, 3-188179 and the like, andthe examples using the silicone polyimide are well-known from JapaneseUnexamined Patent Publication (Kokai) Nos. 61-103927, 63-291922 and thelike. Further, in Japanese Unexamined Patent Publication (Kokai) No.63-291924, the protective coatings of the color filters are suggested tobe made of a curable composition consisting of siloxane polymer andsilicone polyimide. The curable composition described in Japanese KokaiNo. 63-291924 can show relatively superior properties as a protectivecoating of color filters, however, still needs improvements in terms ofcoatability, adhesion properties and a separability as liquid.

Further, the prior art concerning anti-reflective glass havingscattering-preventing properties is as follows: the glass is a materialwhich has been used as a transparent part in a wide variety of articlesfor many years, and glass has been widely utilized in our daily livesowing to its excellent properties such as optical characteristics,mechanical properties, durability and other properties. In recent years,in order to improve visual recognition capability, a reflection-freeglass has been used, in which a metal oxide such as a thin layer ofmagnesium fluoride is deposited or sputtered on a glass part ofelectronic equipments, optical articles, construction or buildingmaterials.

However, it is essential or reflection-free glass, when used in manyfields of use, to always expose the surfaces to the atmosphere. Forexample, when the reflection-free glass is used as a constructionmaterial, particularly those for high-rise buildings, damage of theglass due to earthquakes and other causes will result a very dangeroussituation to the human body, because when the reflection-free grass iscrushed, fragments fall onto the surface of the ground. Further, forindoor use, for example, when the reflection-free glass is used as adisplay of electric equipment, furniture and the like, there is apossibility that the glass crushed due to an unexpected accident causesinjury. Furthermore, when the reflection-free glass is used as a part ofthe large-sized machine equipments in factories, there is a possibilitythat tiny particles of glass may further induce a more serious accident,namely, the degree of danger would be further increased.

Furthermore, in many cases, the adhesive and the applications, such asadhesive tapes, adhesive sheets and others, which relate to the presentinvention are generally used at ordinary room temperature. However, theuse is inevitably limited to a specific range, because the use ofadhesives can result in drawbacks such as separation from a surface ofthe adherend, if the adhesive and the adhesive-applied products areexposed to conditions of high temperature and high humidity.

Thus, as a means for solving the above problems of the adhesive, therehave been suggested

a pressure-sensitive adhesive comprising an acrylic polymer and theincorporated vinyl silane, epoxy silane, methacryl silane or othersilanes,

an adhesive composition comprising an acrylic resin containing ahydroxyl group capable of reacting with an epoxy group and theincorporated epoxy group-containing silane,

an adhesive composition comprising an acrylic resin copolymerized withan ethylenically unsaturated monomer capable of reacting with anisocyanate group and the incorporated isocyanate group-containingorganosilicone compound,

an adhesive composition comprising an acrylic resin having incorporatedtherein a silicate oligomer, and other compositions.

However, the above-mentioned means are insufficient to satisfy therequirements to an adhesion property under a high temperature and highhumidity conditions. Particularly, the means do not provide asatisfactory suggestion concerning the adhesion property between a glasssubstrate and an optical film.

Hitherto, when the plate or sheet glass is packed for a transportationpurposes, wooden frames have been used as a packaging material. However,use of wooden frames causes a remarkable increase of bulk (or volume) ofthe packaged glass, i.e., two or more times of the volume of the plateglass itself to be packed, and contrary to such an increase of bulk, theresulting shock resistance is not always satisfactory to therequirements. Further, foamed plastic sheets, rugged sheets or othersheets have been utilized as packaging materials to transport or storeglass articles or potteries, however, these sheets also can not alwaysprovide a sufficient shock resistance.

When sunlight is irradiated onto various architectural structures or aglass surface thereof, there may be a loss of comfort to the occupantsas a result of an increase of the temperature of the interior space ofthe structures. Further, there is a risk of the human health beingadversely affected due to ultraviolet rays of the irradiated sunlight.Furthermore, because CL an increase of the temperature of the articlesdisposed in the inside of a structure, the articles may cause a changein their color or properties. Thus, there has been an attempt to usefilms capable of cutting or screening the UV rays or near infrared (IR)rays from the sunlight.

A substrate film having applied on a surface of an UV-cut or near IR-cutcoating is well-known as the above-mentioned type of the films, and (1)a method for coating a dye-containing film, (2) a method for coating athin layer containing a metallic compound on a substrate, and (3) amethod for adding an absorbing agent during production of glass or resinto be formed into the substrate, are proposed as the production methods.The principal object of these methods is to reduce transmittance of theUV and near-IR rays by adding a dye or absorbing agent.

However, these methods based on the addition of the dye or absorbingagent can merely retain their effects concerning the fastness only forabout one to two years, because the added dye or absorbing agent per seis deteriorated in properties.

Further, for the prior art UV-cut films, it is difficult for laymen notskilled in the art to correctly laminate the film on a glass surface asthe adherend without causing creases or rumples, and once it has beenlaminated, the film can not be removed from the glass surface.

For the purpose of protecting the surface, the CRTs (cathode ray tubes)have been covered with a hard coated film. The CRTs, however, sufferfrom problems such as adhesion of dust, dirt on the film, anddifficulties in viewing the CRT due to light emitted from fluorescentlamps or a window (reflective projection).

Further, with the increase of the workload of the VDT as a result ofwidespread use of personal computers and word processors, thehealth-hazard due to electromagnetic waves, ultraviolet rays andelectrostatic charges generated or emitted from the CRT devices, as wellas safety measures, have become a serious issue. In order to prevent thereflective protection of fluorescent lamps and light reflection fromwindows to the surface of the CRTs, which is a cause of visualdifficulties, there has been suggested to use an anti-reflective filter,however, the fastening of such an anti-reflective filter to a CRTsurface is troublesome.

As a countermeasure of the above problem, Japanese Unexamined PatentPublication (Kokai) No. 8-112866 teaches the application of ananti-static layer to a hard coated film to be adhered to the CRTsurface, thereby preventing adhesion of dust and the like, and, at thesame time, by forming depressions or projections on the surface of thehard coated film or anti-static layer, thereby obtaining adaze-oreventing effect. However, the anti-static effect has not beensatisfactory and therefore the adhesion of dust, dirt and the like caneasily fire the eye shortly after the application of the anti-staticlayer.

Further, in the prior art hard coated films do not take anycountermeasure against the ultraviolet rays emitted from the displaysurface of a television. The ultraviolet rays can cause a fatigue of theeyes.

Furthermore, recently, the importance of the effect on human health dueto the electromagnetic waves is being made apparent, however, it is trueto say that substantially all of hard coated films and CRT filters inthe prior art do not take measures to protect the human eyes fromelectromagnetic waves and ultraviolet rays emitted from the CRTs.

Generally, plastic lenses have been vulnerable to scratching, andtherefore, in order to prevent scratching, a hard coated layer isusually applied to the surface of the lenses. Further, in order toprevent reflection on the lens surface, an anti-reflective layerconsisting of the deposited inorganic materials is applied to the hardcoated layer. However, plastic lenses having both an applied hard coatedlayer and an anti-reflective layer suffer from the drawback of aremarkably reduced shock resistance in comparison with the plasticlenses without applied layers or the plastic lenses with the hard coatedlayer only.

To solve the above drawbacks, it is well-known to insert a primer layerconsisting of urethane resin between the plastic lens and the hardcoated layer. However, since the urethane resin is formed by the thermalcuring process, several hours for curing time may need until the primerlayer is formed.

Moreover, for primers of the prior art, it was not possible to adjustinterference fringes generated between the lens substrate and the hardcoated layer.

OBJECT OF THE INVENTION

The present invention has an object to provide a resin, which issuitable in the method of producing

a coating for electronic materials;

a glass having both scattering-preventing properties and theanti-reflective properties,

an adhesive agent;

a shock-absorbing material;

an ultraviolet(UV)-cutting sheet;

an ultraviolet-cutting sheet for televisions;

a filter for VDTs and

a high refractive index primer composition as well as a method for theproduction of primer-coated lenses using said primer composition,

the resin has excellent coatability, adhesive properties, storagestability, durability, shock resistance and the like, and isparticularly excellent in a transparency and adhesion property aftercuring of the resin.

The present invention has an object to provide an optical laminatedplate having excellent durability and being more stable in the opticalproperties, the laminated plate using an adhesive which can retain theexcellent adhesion property for an extended period of time under hightemperature and high humidity conditions, and can indicate an excellentadhesion property and durability in the adhesion between a variety ofoptical films and a substrate such as glass.

The present invention has another object to provide an ultraviolet(UV)-curable composition, when is suitable in the formation of coatingsfor electronic materials, such as a surface protective coating ofsemiconductors, an insulating layer of semiconductor-mounted devices, asurface protective coating of color filters of the liquid crystaldisplay devices, an insulating interlayer of multilayered printedcircuits, a protective coating so light guiding materials or phaseshifting materials and other coatings, and which has excellentcoatability, adhesive properties, storage stability, and also hasexcellent transparency properties.

The present invention has an object to provide a glass having ascattering-preventing function along with an anti-reflective function,thereby increasing the safety of the reflection-free glass.

The present invention has vet another object to provide ashock-absorbing material having a high shock resistance, which cangreatly reduce the volume, and increases the efficiency oftransportation, and also enables a simpler packing method.

The present invention has an object to provide an ultraviolet-cuttingsheet, which can be easily fixed and removed by laypersons, can berepeatedly used for many times, exhibits an excellent transparency andlight fastness, has a high transmittance of visible radiations, and caneffectively cut the ultraviolet rays.

The present invention has yet another object to provide anultraviolet-cutting filter for a television, which can effectively cutthe ultraviolet rays without reducing transmittance of the visibleradiations, and can curb uneven color shading, can prevent thegeneration of electrostatic charges, and can be easily attached andremoved.

The present invention has another object to provide anultraviolet-cutting filter for VDTs, which can cut the ultraviolet rayswhile maintaining a transmittance of the visible radiations, can shieldthe electromagnetic waves, can prevent the generation of electrostaticcharges, and can be easily attached and removed.

The present invention has another object to provide a primer compositionwhich enables formation of a primer layer within a shortened period oftime, can increase a shock resistance of the plastic lenses, and carreduce interference fringes produced between the lens substrate and thehard coated layer, and a primer-coated lens with the primer layer.

SUMMARY OF THE INVENTION

The transparent resin having an adhesion property according to thepresent invention comprises a cured product of polymerizing compositionwhich comprises at least one of diallyl phthalate, diallyl isophthalateand diallyl terephthalate, and pentaerythritoltetra(3-mercaptopropionate).

In the above polymerizing composition, it is preferable that the atleast one of diallyl phthalate, diallyl isophthalate and diallylterephthalate, and the pentaerythritol tetra(3-mercaptopropionate) arecontained in a ratio of 2:1 to 1:3 with regard to an equivalent ratio.The cured product is preferably produced by polymerizing thepolymerizing composition by means of a photopolymerization initiator;and the amount of photopolymerization initiator is preferably 0.005 to10% by weight. Further, an ultraviolet curing agent may be used as thephotopolymerization initiator.

In the adhesive transparent resin according to the present invention, anultraviolet-absorbing agent or a refractive index-controlling materialmay be added as, for example, a substance for modifying opticalproperties and others to the polymerizing composition. It is preferablethat the ultraviolet-absorbing agent is contained in an amount of 0.01to 3.0% by weight. Also, it is possible to use a metallic compound asthe refractive index-adjusting material.

The adhesive transparent resin of the present invention is characterizedby laminating another functional layer having different physicalproperties from those of the resin, thereby forming a composite.Suitable functional layers include an anti-reflective layer, an opticalfilter, a plastic film and the like.

The adhesive or adhesive agent according to the present inventioncomprises a photocured product of the polymerizing composition whichcomprises at least one of diallyl phthalate, diallyl isophthalate anddiallyl terephthalate, and pentaerythritol tetra(3-mercaptopropionate)in an equivalent ratio of 2:1 to 1:3.

The present invention provides an optical laminated plate characterizedby laminating a substrate and an optical film layer through an adhesivelayer consisting of the above-mentioned adhesive.

Further, the present invention provides an optical laminated filmcomprises an optical film layer, an adhesive layer consisting of theabove-mentioned adhesive and a releasable film layer.

The feature of the present invention resides in the fact that acomponent capable of functioning as an adhesive without usingconventional materials, such as an acrylic resin and a siliconecompound, is found. Using the adhesive of the present invention, itbecomes possible to maintain a very excellent adhesion property for along period under the high temperature and high humidity, and also toprovide an optical laminate having an excellent durability with regardto the adhesion property between the glass substrate and the opticalfilms, and showing a fewer fluctuation in the optical properties.

In the production of the photocured product of the present invention,ultraviolet rays are generally used, however, electron beams and thelike may be used to initiate curing.

The coating- or film-forming photocurable composition of the presentinvention is made based on the inventors' attention that diallylphthalate can form a coating, and simultaneously showing a heatresistance and a transparency. The inventors have found that if acertain sulfur compound is incorporated into the diallyl phthalate, apolymerization product with a three-dimensional structure having anexcellent adhesion property is produced by the simple polymerizationreaction using light or ultraviolet ray.

That is, the coating-forming photocurable composition of the presentinvention is characterized by adding a photopolymerization initiator inan amount of 0.005 to 10% by weight to a polymerizing composition whichcomprises at least one of diallyl phthalate, diallyl isophthalate anddiallyl terephthalate, and pentaerythritol tetra(3-mercaptopropionate)in an equivalent ratio of 2:1 to 1:3.

The anti-reflective glass with the scattering-preventing functionaccording to the present invention is to solve the above-mentionedproblems by using the specific adhesive when a film having the givenanti-reflective function is laminated onto the conventional glass.

That is, the anti-reflective glass with the scattering-preventingfunction according to the present invention is characterized bycomprising a glass having applied to at least one surface of an adhesivelayer, a plastic film layer and an anti-reflective layer in this orderfrom the one surface. The adhesive layer comprises a photocurablecomposition which comprises a monomeric mixture of at least one ofdiallyl phthalate, diallyl isophthalate and diallyl terephthalate, andpentaerythritol tetra(3-mercaptopropionate) in an equivalent ratio of2:1 to 1:3; and a photopolymerization initiator of 0.005 to 10% byweight being added to the monomeric mixture.

The shock-absorbing material according to the present invention ischaracterized by comprising a sheet-like photocured product ofpolymerizing composition which comprises a monomeric mixture of at leastone of diallyl phthalate, diallyl isophthalate and diallylterephthalate, and pentaerythritol tetra(3-mercaptopropionate) in anequivalent ratio of 2:1 to 1:3; and a photopolymerization initiator of0.005 to 10% by weight being added to the monomeric mixture.

The present invention also provides a shock-absorbing material in whicha film is laminated onto a single surface of the sheet-like photocuredproduct.

The ultraviolet-cutting sheet according to the present invention iscompleted based on the findings that a photocurable resin having thespecific composition can exhibit an excellent flexibility along with anUV cutting effect, can be semi-permanently brought in close contact witha plane surface without using an adhesive agent, and also can beoptionally released from the adherend in a simple method.

That is, the ultraviolet-cutting sheet of the present invention ischaracterized by comprising a photocured product of polymerizingcomposition which comprises a monomeric mixture of at least one ofdiallyl phthalate, diallyl isophthalate and diallyl terephthalate, andpentaerythritol tetra(3-mercaptopropionate) in an equivalent ratio of2:1 to 1:3; and a photopolymerization initiator of 0.005 to 10% byweight being added to the monomeric mixture.

The present invention further provides an ultraviolet-cutting sheet inwhich an anti-reflective layer is applied on a single surface of thephotocured product.

The ultraviolet-cutting filter for televisions according to the presentinvention is completed based on the findings that a photocurable resinhaving the specific composition can cut UV rays, prevent the generationof electrostatic charges and also exhibit an excellent flexibility, canbe semi-permanently brought in close contact with a plane surfacewithout using an adhesive agent, and also can be optionally releasedfrom the adherend in a simple method.

That is, the ultraviolet-cutting sheet for televisions according to thepresent invention is characterized by comprising a photocured product ofpolymerizing composition which comprises a monomeric mixture of at leastone of diallyl phthalate, diallyl isophthalate and diallylterephthalate, and pentaerythritol tetra(3-mercaptopropionate) in anequivalent ratio of 2:1 to 1:3; and a photopolymerization initiator of0.005 to 10% by weight being added to the monomeric mixture.

The present invention further provides an ultraviolet-cutting sheet fortelevisions in which an anti-reflective layer is applied on a surface ofthe photocured product.

The filter for visual display terminals (VDTs) according to the presentinvention is completed based on the findings that a deposition layer ofindium-tin oxide can exhibit an electromagnetic waves-shielding propertyand an ultraviolet-curable resin having the specific composition can cutUV rays, prevent the generation of electrostatic charges and alsoexhibit an excellent flexibility, can be semi-permanently brought inclose contact with a plane surface without using an adhesive agent, andalso can be optionally released from the adherend in a simple method.

That is, the VDT filter according to the present invention ischaracterized by comprising a substrate film having applied on onesurface thereof a deposition layer of indium-tin oxide and on the othersurface thereof a flexible resin layer which comprises a photocuredproduct of polymerizing composition, the polymerizing compositioncomprising a monomeric mixture of at least one of diallyl phthalate,diallyl isophthalate and diallyl terephthalate, and pentaerythritoltetra(3-mercaptopropionate) in an equivalent ratio of 2:1 to 1:3; and aphotopolymerization initiator of 0.005 to 10% by weight being added tothe monomeric mixture.

Further, the VDT filter of the present invention may have ananti-reflective layer on the deposition layer of indium-tin oxide.

The high refractive index primer composition according to the presentinvention is completed based on the findings that use of theultraviolet-curable resin enables to form a film or coating within ashortened time, and incorporation of a sol of metallic compound having ahigh refractive index enables to reduce interference fringes.

That is, the high refractive index primer composition of the presentinvention comprises 60 to 95% by weight of the photocurable polymerizingcomposition and 5 to 40% by weight of a sol of metallic compound havinga high refractive index.

In addition, the process for the production of primer-coated lensesaccording to the present invention is characterized by coating theabove-mentioned primer composition on a substrate of plastic lens,followed by ultraviolet irradiation, to form a primer layer or coating.

In addition, the present invention is directed to a combination of atleast one fragile article and a shock-absorbing material, the shockabsorbing material comprising a photocured product of polymerizingcomposition in a form of a sheet which comprises a monomeric mixture ofat least one of diallyl phthalate, diallyl isophthalate and diallylterephthalate, and pentaerythritol tetra(3-mercaptopropionate) in anequivalent ratio of 2:1 to 1:3; and a photopolymerization initiator of0.005 to 10% by weight being added to the polymerizing composition.

Still further, the present invention is directed to anultraviolet-cutting sheet, comprising a photocured product ofpolymerizing composition which comprises a monomeric mixture of at leastone of diallyl phthalate, diallyl isophthalate and diallylterephthalate, and pentaerythritol tetra(3-mercaptopropionate) in anequivalent ratio of 2:1 to 1:3; and a photopolymerization initiator of0.005 to 10% by weight being added to the monomeric mixture, the sheethaving opposing surfaces, and either of said opposing surfaces beingcapable of being applied to a surface.

Still further, the present invention is directed to anultraviolet-cutting sheet for televisions comprising a photocuredproduct of polymerizing composition which comprises a monomeric mixtureof at least one of diallyl phthalate, diallyl isophthalate and diallylterephthalate, and pentaerythritol tetra(3-mercaptopropionate) in anequivalent ratio of 2:1 to 1:3; and a photopolymerization initiator of0.005 to 10% by weight being added to said polymerizing composition, thephotocured product being in a form of a sheet having opposing surfaces,and either of the opposing surfaces being capable of being applied to asurface.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of the anti-reflective glass with thescattering-preventing function according to the present invention.

FIG. 2 is a cross-sectional view of the filter for VDTs illustrating onepreferred embodiment of the present invention.

FIG. 3 is a graph showing the electromagnetic waves-shielding effectprovided by the filter for VDTs produced in Example 23.

FIG. 4 is a graph showing the electromagnetic waves-shielding effectprovided by the filter for VDTs produced in Example 24.

FIG. 5 is a graph showing the electromagnetic waves-shielding effectprovided by the filter for VDTs produced in Example 25.

FIG. 6 is a graph showing the electromagnetic waves-shielding effectprovided by the filter for VDTs produced in Example 26.

DESCRIPTION OF REFERENCE NUMERALS

1 glass

2 adhesive layer

3 layer of plastic film

4 anti-reflective layer

11 substrate film

12 flexible resin layer

13 deposition layer of indium-tin oxide

14 anti-reflective layer

PREFERRED EMBODIMENTS OF THE INVENTION

The inventors have paid their attention upon the fact that diallylphthalate can form a coating exhibiting both of a heat resistance and atransparency, and then have found that if a certain sulfur compound isincorporated into diallyl phthalate, it becomes possible to use a simplepolymerization reaction, thereby producing a transparent polymerizationproduct having a three-dimensional structure and exhibiting an excellentrepeatability of adhesion. Consequently, the inventors have completedthe present invention.

Hereinafter, the present invention will be described in detail

In the polymerizing composition of the present invention, as themonomers, at least one member selected from diallyl phthalate, diallylisophthalate and diallyl terephthalate as a diallyl component, andpentaerythritol tetra(3-mercaptopropionate) as a functionalgroup-containing component are used in an equivalent ratio of 2:1 to1:3. If the both monomers are blended in a ratio other than theabove-described range of the equivalent ratio, unpolymerized componentsin the form of liquid are remained in the polymerization product becauseof incompletion of the polymerization reaction. Further, if the amountof at least one of diallyl phthalate, diallyl isophthalate and diallylterephthalate as the diallyl component is increased above said range ofthe equivalent ratio, the polymerization can not be completed.Furthermore, if the amount of pentaerythritol tetra(3-mercaptopropionate) is excessively increased, the resultingpolymerization product will give a strong odor of the monomers used.

In view of the polymerization reaction and uniformity of the curedproduct, it is more preferred that the diallyl component and thefunctional group-containing component are used in an equivalent ratio of1.1:1 to 1:1.1.

To the monomeric mixture satisfying the above-mentioned equivalentratio, a photopolymerization initiator is added for the purpose ofcausing a polymerization reaction upon lights or ultraviolet rays. It ispreferred that the amount of the photopolymerization initiator added isso controlled that it is contained in the polymerizing composition in anamount of 0.005 to 10% by weight. The photopolymerization initiator ofless than 0.005% by weight will not ensure a polymerization reactionsufficient for curing, and a adhesion property will be insufficient. Theamount of addition above 10% by weight will cause a sudden reaction uponaddition of the photopolymerization initiator, thereby losing astability as a solution. If these drawbacks have happened, they willbecome a cause of serious troubles in the production plants.

The photopolymerization initiator is not restricted to the specific one,and accordingly a wide variety of photopolymerization initiators may beused in the practice of the present invention. Typical examples ofphotopolymerization initiators include benzoin, benzyl, benzoin methylether, acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one,1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone,1-hydroxycyclohexyl phenylketone, 2,2-dimethoxy-2-phenylacetophenone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-procane-1-one,2-benzyl-2-dimethylamino-1-(4-morpnol-nophenyl)-butane-1-one,benzophenone, 4,4′-bis(dimethylamino)benzoprhenone,4,4′-bis(dethylamino)benzophenone, N,N-dimethylaminoacecophenone,2-methylanthraquinone, 2-ethylanthraquinone, 1-chioroanthraquinone,2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone,2,4,6-trichloromethyl-s-triazine,2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tiazine,2,4-bis(trichloromethyl)-4′-methoxyphenyl-s-triazne,2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-p-methoxystyryl-4,6-bis(trichloromethyl)-s-triazine,2-(2′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazolyl,2,2′-bis(o-chloroohenyl)-4,4′,5,5′-tetra(p-methoxyphenyl)bisimidazolyl,2,4,6-trimethylbenzoyldiprenylphosphine oxide, bisacylphosphine oxide,triphenylphosphine, triphenylphosphite, trilauryl-trithiophosphite,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,(η5˜2,4-cyclopentadiene-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl)benzene]-iron(1+)-hexafluorophosphite(1−)and the like. These photopolymerization initiators may be used alone oras a combination or two or more.

Among the above-listed photopolymerization initiators, it isparticularly preferred to use 2-hydroxy-2-methyl-1-phenylpropane-1-oneand bisacylphosphine oxide in combination.

Further, these photopolymerization initiators may be used in combinationwith any one or two or more of the well-known photosensitizing agentssuch as N,N-dimethylaminobenzoic acid ethyl ester,N,N-dimethylaminobenzoic acid isoamyl ester, triethanol amine,2-mercaptobenzcthiazole, 2-mercapto benzooxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methylthio-1,3,4-thiazole and the like.

For the present invention, the polymerizing composition may be usedafter dilution with a solvent for the purpose of increasing itscoatability and for the purposes of controlling its viscosity anduniformly mixing the components. The organic solvent which can be usedherein is not restricted to the specific one, and in view of obtaining acoating composition having a good coatability, it includes organicsolvents, for example, 3-methyl-3-methoxybutanol, propylene glycolmonomethyl ether, dipropylene glycol monomethyl ether, tripropyleneglycol monomethyl ether, ethyl cellosolve, methyl cellosolve, methylcarbitol, ethyl carbitol and the like.

In addition, the organic solvent includes a hydrocarbon solvent such asn-hexane, n-decane, cyclohexane and the like, an aromatic hydrocarbonsolvent such as benzene, toluene, xylene and the like, an ester solventsuch as butyl acetate, benzyl acetate and the like, an alcoholic solventsuch as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcarbitol, ethyl carbitol, butyl carbitol, methyl cellosolve acetate,ethylene glycol, diethylene glycol and the like, a ketone solvent suchas methyl ethyl ketone, and derivatives thereof.

In practice of the present invention, in addition to the above-describedpolymerizing composition (monomeric mixture) and photopolymerizationinitiator as the essential components, any additive such as a stabilizeror stabilizing agent, a curing accelerator, a defoaming agent, aleveling agent, a surface active agent, an ultraviolet (UV)-absorbingagent, pigments and the like may be used, if necessary.

In the present invention, to the monomeric mixture having the describedequivalent ratio, an UV-absorbing agent may be added in an amount of0.01 to 3.0% by weight, if necessary. If the amount of the UV-absorbingagent added is less than 0.01% by weight, a satisfactory UV-absorbingeffect car not be obtained, and the UV-absorbing agent beyond 3.0% byweight results in saturation thereof, thereby not dissolving in themonomeric mixture.

The UV-absorbing agent is not restricted to the specific one, insofar asit can be dissolved in either or both of the above-mentioned monomers,and accordingly a wide variety of UV-absorbing agents may be used.Usable UV-absorbing agents include, for example, benzophenones such as2-hydroxybenzophenone, 2,4-dihydroxybenzophenone and the like,salicylates such as phenylsalicylate and the like, benzotriazoles suchas (2′-hydroxyphenyl)benzotriazole,(2′-hydroxy-5′-methylphenyl)benzotriazole,2,2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol]and the like, and cyanoacrylates such asethyl-2-cyano-3,3-diphenylacrylate and the like. These UV-absorbingagents may be used alone or as a combination of two or more agents.

The coating-forming UV-curable composition of the present invention isconstituted from the monomeric mixture described in the paragraph number[0035] and the photopolymerization initiator described in the paragraphnumber [0036]. The composition of the present invention has an excellentcoatability and storage stability, and can be cured or hardened uponirradiation of UV rays after it is coated on the substrate and others.The thus-produced cured coating has both of a heat resistance and atransparency, is excellent in an adhesion property, and also isexcellent in electrical properties, particularly an insulating property,and therefore the cured coating can be utilized as an insulating layerfor semiconductor-mounted devices, a passivation layer, a buffer layer,an insulating interlayer for the multilayered printed circuits or thesemiconductor integrated circuits, and a protective coating of thewaveguide materials and the phase shifting materials.

Further, when the cured coating is used as a protective coating of thecolor filters, a transparent protective coating can be produced bycoating a polymerizing composition of the present invention over acoloring layer on the transparent substrate such as glass and the likeand, if necessary, over a light-shielding layer provided in a gapbetween the coloring layers, and by curing the coated composition.

The anti-reflective glass with the scattering-preventing function willbe described with reference to the accompanying drawing.

FIG. 1 is a cross-sectional view of the anti-reflective glass with thescattering-preventing function according to the present invention. Theanti-reflective glass with the scattering-preventing function using theadhesive resin of the present invention has, on a single surface or bothsurfaces of the glass 1, an adhesive layer 2, a plastic film layer 3 andan anti-reflective layer 4 in this order.

The glass used in the present invention is completely free fromrestrictions with regard to its configuration, properties of thematerial and others.

In the present invention, a photocurable composition comprising themonomeric mixture described in the paragraph number [0035] having addedthereto the photopolymerization initiator described in the paragraphnumber [0036]. A thickness of the adhesive layer 2 is generally in therange of 1 to 100 μm, preferably 10 to 90 μm. The thickness of theadhesive layer of less than 1 μm can not exhibit a satisfactory adhesionpower, and the thickness above 100 μm can deteriorate a smoothess of theadhesive layer.

Further, films of, for example, polyesters such as polyethyleneterephthalate, polybutylene terephthalate, polyethylene naphthalate,polyethylene terephthalate-isophthalate copolymers and the like,polyacrylates, polyurethanes, polyolefines such as trimethylpentene andthe like, polyamides, polycarbonaces, acetyl celluloses such astriacetyl cellulose, diacetyl cellulose, acetate butylate cellulose andthe like, polyether sulfons, polysulfons, polyethers, polyether ketones,poly(meta)acrylonitrile and others may be used as the plastic film layer3. These films are generally used as a colorless and transparent film,however, depending upon the fields of utilization of thescattering-preventing antireflective glass, they may be colored or theymay contain the designs or patterns.

Furthermore, a thickness of the plastic film layer 3 is generally in therange of 10 to 500 μm, preferably 50 to 450 μm. The thickness of lessthan 10 μm causes a difficulty in obtaining a smoothness necessary asthe scattering-preventing antireflective glass, and the thickness above500 μm can deteriorate a flexibility (pliability, ease of bending),thereby causing a difficulty of handling (operation).

For the antireflective glass with the scattering-preventing functionformed according to the present invention, an antireflective layer 4 isapplied over the plastic film layer 3, namely, as an outermost layer.The anti-reflective layer is not particularly limited, and, for example,it can be formed from one or two or more inorganic materials such astitanium oxide, magnesium fluoride, aluminum oxide, silicon oxide,tantalum oxide, diantimony pentaoxide, indium oxide, yttrium oxide,ytterubium oxide, zirconium oxide, cerium fluoride, cerium oxide,lanthanum fluoride, lanthanum oxide, stannic oxide and the like bydepositing these materials or alternatively from organic materials suchas fluorine-containing compounds, silane compounds and the like byapplying these materials as a thin layer which, as applied, can be usedas the antireflective layer or by curing these materials with electronbeams, ultraviolet rays, heat or the like. The antireflective layer maybe formed either as a single layer or as a multilayer from theabove-mentioned materials, and it is preferred that its thickness is sodesigned that the thickness equals to a wavelength of visible radiationsor a half or less of said wavelength, although the thickness may bevaried depending upon the used glass and layer constitutions. [0046]

For the production of the antireflective glass with thescattering-preventing function formed according to the presentinvention, a plastic film with the previously applied antirellectivelayer may be prepared, and after by adhering the plastic film to theglass, or alternatively, after adhesion of a film onto the glass, anantireflective layer may be formed over the film. In each case, anoutermost layer must always be an antireflective layer.

As an means for adhesion of the glass and the plastic film, there are amethod in which an adhesive agent consisting of an adhesive resinaccording to the present invention is coated on a surface of the glass,a plastic film is applied over the coated adhesive agent, and then theadhesive agent is photocured, and a method in which a plastic film withthe coated adhesive agent consisting of an adhesive resin is appliedonto a surface of the glass, and then the adhesive agent is photocured.

The thus-produced glass according to the present invention has afunction of preventing the broken glass from scattering, and thusensures safety of the human body and others, because the broken glasscan be kept on the plastic film due to a high adhesion property of thecured adhesive agent to both the glass and the plastic film, when theglass is broken due to an accidental trouble and the like.

The adhesive agent according to the present invention may be used forthe adhesion of optical films having optical properties such as apolarizing film and other films. The adhesive agent comprises themonomeric mixture described in the paragraph number [0035]. For thepurpose of inducing a photopolymerization and curing reaction, thephotopolymerization initiator described in the paragraph number [0036]is incorporated in the adhesive agent.

The adhesive agent of the present invention is obtained by blending eachof the above-described components in a dark room to prepare apolymerizing composition, and the resulting composition is irradiatedwith light to cause a polymerization and curing reaction of theadhesive, thereby producing a photocured product. Typically, theresultant polymerizing composition is subjected to light irradiation,after it is molded into a film, a sheet and other configurationsdepending upon the specific use of the adhesive agent.

The method of forming and curing the polymerizing composition to obtaina photocured product is not restricted to the specific one, and itincludes, for example, a method of coating a solution of thepolymerizing composition at a predetermined thickness on a substrate,followed by light irradiation, a method of pouring a solution of thepolymerizing composition into a predetermined mold, followed by lightirradiation, and other methods.

Typically, ultraviolet rays are used as the irradiation light, butelectron beams may be used, as an alternative. The conditions of thelight irradiation are not restrictive, and therefore thoseconventionally used in the well-known prior art methods may be adopted.

The adhesive agent of the present invention may be used in the adhesionof optical films having optical properties such as a polarizing film andthe like. For example, the adhesive agent can be conveniently used inthe adhesion between an optical film and a substrate such as a glassplate and the like.

The optical laminated plate formed by using an adhesive agent consistingof a cured product of the polymerizing composition is a laminate orlaminated product produced by laminating a substrate and an optical filmlayer through an adhesive layer consisting of the adhesive agent of thepresent invention.

An optical film for constituting the optical film layer is notrestricted to the specific one, insofar as the selected film has opticalproperties, but preferably polymeric films such as a polarizing film, aphase difference film, an elliptic polarizing film and the like are usedas the optical film A thickness of the optical film is not restrictive,and it is preferred that each film has a thickness of about 25 to 250μm.

The polarizing film includes polarizing films using polyvinyl alcohol,polarizing films using polyvinyl formal, polarizing films usingpolyvinyl acetal and others.

Preferably, the biaxially oriented films (degree of orientation: 2 to 10times, preferably 4 to 7 times) produced from a raw film consisting of apolyvinyl alcohol resin having an average polymerization degree of 1500to 10000 and a saponification degree of 85 to 100% by mole by dyeing thefilm with an acueous solution of iodine-potassium iodide or a dichromicdye are used as the polarizing film.

As the phase difference film, polymeric films such as those of polyvinylalcohols, polycarbonates, polyesters, polyallylates, polyimides,polyolefines, polystylenes, polysulfons, polyether sulfons, triacetylcellulose resins, cyclic polyolefines, cellulose acetate, polyvinylchloride, saponification products of ethylene-vinyl acetate copolymerand the like are used. Principally, polycarbonate or polyvinyl alcoholfilms are used.

The elliptic polarizing film is a combination of a polarizing film and aphase difference film. These films may be used after one type or two ormore types of the films are laminated.

The substrate used herein is not restricted to the specific one, and itincludes a metal plate such as a stainless steel plate, aluminum plate,steel plate and the like, a decorative plate or laminate of thesynthetic resin such as a polyethylene plate, polypropylene plate,melamine resin plate, phenol resin plate and the like, a plate-shapedmaterial such as a plywood, wood veneer, glass plate and the like, arod-shaped material, a cut and polished article, an injection moldedarticle, a protective material and others.

Among the above-described materials, the effects of the presentinvention will be remarkably exhibited, when the glass plate isparticularly used as the substrate. A thickness of the substrate is notrestrictive, and it is preferably in the range of about 1 to 100 mm.

The method for producing the optical laminated plate is not restrictive.For example, the optical laminated plate can be obtained by applying alayer consisting of the adhesive agent of the present invention onto anoptical film which will be described hereinafter, and further applying arelease film layer onto the applied adhesive layer, thereby forming anoptical laminated film. Before use, the optical laminated film issuitably cut, and the cut laminated film is adhered to the substrateafter the release film is removed therefrom. Alternatively, theproduction method of the optical laminated plate includes a method inwhich an adhesive layer consisting of the adhesive agent of the presentinvention is formed by coating the above-described polymerizingcomposition onto a substrate and then irradiating the coating withlights such as ultraviolet rays and the like, and then an optical filmis pressed and laminated to an adhesive layer side of the substrate bymeans of rollers and the like.

The laminated plate produced by using the adhesive agent of the presentinvention, if the above-described adhesive agent based on thetransparent resin of the present invention is used, can ensure anoptical laminated plate which does not generate any defects inappearance such as foaming or peeling of the adhesive layer during itsuse at a high temperature and a high humidity, exhibits an excellentheat resistance and humidity resistance, and also has excellent opticalproperties such as radiation permeability and the like. Such opticallaminated plate can be used as a liquid crystal display device,sunglasses, daze-free or glare-proofing glasses and the like.

When the laminated plate produced according to the present invention isused as a liquid crystal display device, the optical laminated plate canbe applied to the liquid crystal display device, after it is prepared bylaminating a liquid crystal cell and a polarizer (polarizing film) byusing the adhesive agent of the present invention. The liquid crystalcell has a structure in which a liquid crystal is sandwiched between twoglass substrates, each of which has a transparent electrode coated on asurface of the substrate, and a molecular orientation layer formed onthe electrode.

The optical laminated film of the present invention is a laminated filmhaving an optical film layer and an adhesive layer.

The optical laminated film of the present invention is obtained by usingoptical films such as the above-described polarizing film, phasedifference film eliptic polarizing film and the like as a base orsubstrate and laminating an adhesive layer constituted from the adhesiveagent, consisting of the adhesive resin, of the present invention. Themeans for applying the adhesive layer includes, for example, a method inwhich the above-described polymerizing composition of the presentinvention is coated on the base, and thereafter the coated compositionis irradiated with lights to obtain a photocured product.

The optical laminated film of the present invention can be cut to obtaina configuration required for use, thereby forming an optical laminatedplate. The cut film is adhered through its adhesive layer to a glass orother substrates described above as an adherend.

In addition, if required, a layer of the release film or the like may befurther applied over the adhesive layer of the laminated film (a sideopposed to the optical film layer). The application of the release filmlayer enables to obtain an optical laminated film having an excellentconvenience, because the optical laminated film can be adhered to asubstrate such as glass and the like, after it is cut to a requiredconfiguration and then the release film layer is suitably separated fromthe cut film. The material for forming the release film layer includespolyesters such as polyethylene terephthalate, polyethylene naphthalateand the like, polyolefines such as polyethylene, polypropylene and thelike, polyvinyl halides such as polyvinyl chloride, polyvinylidenechloride and the like, and others.

The method of forming an adhesive layer and a release film layer on thesubstrate includes a method in which an adhesive layer is applied on arelease film and then an optical film is laminated on the appliedadhesive layer, a reverse method in which an optical film is used as asubstrate, an adhesive layer is applied on the film substrate and then arelease film is laminated on the applied adhesive layer, and others. Thethus obtained optical laminated film can be laminated to glass or othersubstrates as the adherend, after the laminated film is cut to arequired shape before use, and the release film is peeled from the same.

The shock-absorbing material according to the present inventioncomprises a sheet-like ultraviolet (UV)-cured product of thepolymerizing composition which comprises the monomeric mixture describedin the paragraph number [005] having added thereto thephotopolymerization initiator described in the paragraph number [0036].

Further, for the present invention, if necessary, a stabilizer orstabilizing agent may be added in an amount of 0.01 to 3.0% by weight tothe monomeric mixture having the above-described equivalent ratio. Theamount of the stabilizing agent added of less than 0.01% by weight doesnot ensure a light stability of the mixed solution, and the amount ofabove 3.0% by weight causes a difficulty of dissolution of the addedagent.

The stabilizing agent is not restrictive, insofar as it can be dissolvedin either or both of the monomers used. A variety of the stabilizingagents may be used, and include, for example, the UV-absorbing agentdescribed in the paragraph number [0040]. These stabilizing agents maybe used alone or by combining two or more agents.

The sheet-like cured product based on the adhesive resin, which isobtained by irradiating the above-described polymerizing compositionwith ultraviolet rays, and by molding into a sheet-like product, has ahigh transparency and an excellent flexibility. A thickness of thesheet-like UV-cured product may be widely varied depending upon types ofthe articles to be protected and objects in use of the shock-absorbingmaterial (transport, keeping and the like), and typically the thicknessis preferably in the range of 0.01 to 5 mm, more preferably in the rangeof 0.05 to 3 mm. The thickness of the sheet-like UV-cured product ofless than 0.01 mm does not ensure a satisfactory shock-absorbing effect,and the thickness of above 5 mm may reduce a workability.

The shock-absorbing material of the present invention may be thoseobtained by laminating a film on a single surface of the sheet-likeUV-cured product. The lamination of the film on the single surface ofthe UV-cured product makes easy to peel off one sheet from others at afilm surface when a package is opened, after sheets of glass arelaminated and packed to make the package, because the UV-cured productused in the present invention has a property of closely fixing to glass.The film is not restricted to the specific one and includes films ofpolyesters such as polyethylene terephthalate and the like, films ofpolyolefines such as polyethylene, polypropylene and the like, films ofpolyvinylidene chloride and the like, and other films.

The film typically has a thickness of 10 to 400 μm, preferably 20 to 200μm. The film thickness of less than 10 μm results in a reduction of thestrength, and the thickness or above 400 μm does not ensure winding ofthe film during production.

The shock-absorbing material having the above-described laminatestructure can be produced by coating on a film a polymerizingcomposition prepared by blending each of the above-described components,and causing a polymerization and curing reaction of the composition uponUV irradiation, thereby forming a layer consisting of the UV-curedproduct having an excellent flexibility.

The UV-cutting sheets according to the present invention are thoseproduced by mixing the monomeric mixture described in the paragraphnumber [0035] with the UV-absorbing agent described in the paragraphnumber [0040] and the photopolymerization initiator described in theparagraph number [0036].

Upon UV irradiation to the polymerizing composition containing each ofthe above-described components as described above, thereby causing apolymerization and curing reaction of said composition, there isobtained an UV-cured resin having a high transparency. Moreover, thethus obtained UV-cured resin has an excellent flexibility and asheet-like molded article thereof can be adhered to a glass surface or adisplay surface of the televisions without using an adhesive and otheraids The adhesion of the molded article can be semi-permanent. Further,the adhered article can be easily separated by hand, and also theadhesion and separation of the article can be repeated again and again.

Molding of the UV-cured resin can be carried out by using any well-knownmethods, for example, extrusion molding method and calendaring methodsuch as die method, inflation method, coextrusion method, extrusionlamination method and the like, for example, roll coating method,spraying method and the like.

Typically, in view of ease of handling and adhesion property, theUV-cutting sheets and UV-cutting filters for televisions formed from theabove-described UV-cured product preferably have a thickness of 0.01 to2 mm, more preferably a thickness of 0.1 to 1 mm.

An antireflective layer may be further applied to the UV-cutting sheetsof the present invention. The material for forming the antireflectivelayer includes ZnO, TiO2, CeO2, Sb2O5, SnO2, ZrO2, Al2O3, andlow-refractive index materials such as MgF2, SiO x (1.50≦x≦2.00), LiF,3NaF—AlF3, AlF3, Na3AlF6 and the like. The antireflective layer can beformed by any optional method such as vacuum deposition method,sputtering method, ion plating method, ion beam assisted method and thelike.

For the present invention, it is preferred that a thickness of theantireflective layer is so designed that a layer portion using thehigh-refractive index materials has a thickness of λ/2 and a layerportion using the low-refractive index materials has a thickness of λ/4,in which λ means 550 nm.

The UV-cutting television filters of the present invention are producedby mixing the monomeric mixture described in the paragraph number [0035]with the UV-absorbing agent described in the paragraph number [0040] andalso the photopolymerization initiator described in the paragraph number[0036].

Upon UV irradiation to the polymerizing composition containing each ofthe above-described components incorporated as described above, therebycausing a polymerization and curing reaction of said composition, thereis obtained an UV-cured resin having a high transparency. Moreover, theUV-cured resin has an excellent flexibility and a sheet-like moldedarticle thereof can be adhered to a display surface of the televisionswithout using an adhesive and the like. The adhesion of the moldedarticle can be semi-permanent. Further, the adhered article can beeasily separated by hand, and also the adhesion and separation of thearticle can be repeated again and again.

Molding of the UV-cured product can be carried out by using anywell-known method such as roil coating method, spraying method andothers.

In view of ease of handling and adhesion property, it is generallypreferred that the UV-cutting television filters made from theabove-described UV-cured product have a thickness of 0.01 to 2 mm, morepreferably a thickness of 0.1 to 1 mm. [0071]

Further, the UV-cutting television filters of the present invention,although they do not use an anti-static agent, can inhibit generation ofelectrostatic charges, and therefore they can prevent undesirableadhesion of trashes and dusts to the filters and electric shock due tothe generated electrostatic charges.

For the UV-cutting television filters of the present invention, anantireflective layer may be further applied thereto. The material forforming the antireflective layer includes high-refractive indexmaterials, for example, ZnO, TiO2, CeO2, Sb2O5, SnO2, ZrO2, Al2O3 andthe like, and low-refractive index materials, for example, MgF2, SiO x(1.50≦x≦2.00), LiF, 3NaF—AlF3, AlF3, Na3AlF6 and the Like. Theantireflective layer can be formed in accordance with any optionalmethod such as vacuum deposition method, sputtering method, ion platingmethod, ion beam assisted method and the like.

In the practice of the present invention, it is preferred that athickness of the antireflective layer is so designed that a layerportion using the high-refractive index materials has a thickness of λ/2and a layer portion using the low-refractive index materials has athickness of λ/4, in which λ means 550 nm.

The filters for visual display terminals (VDTs) of the presentinvention, as described in the above, have a deposition layer ofindium-tin oxide (ITO) on one surface of the substrate film, and aflexible resin layer, formed from the specified UV-cured product, onanother surface of the substrate film.

The substrate film used herein is not limited to the specific one, if itis a transparent film, and it includes polyester films such aspolymethyl methacrylate films, polycarbonate films, polyethyleneterephthalate films and the like; polyolefin films such as polyethylenefilms, polypropylene films and the like; cellulose films such asnitrocellulose films, acetylcellulose films, cellulose acetatepropionate films, ethylhydroxy ethylcellulose films and the like;polyvinylidene chloride films; polyvinyl chloride films; polystyrenefilms and others.

Typically, the substrate film has a thickness of 10 to 400 μm,preferably 25 to 200 μm. When the substrate film has a thickness of lessthan 10 μm, the mechanical strength is reduced. The film thickness above400 μm causes a problem that the film can not be wound during theproduction process.

In the filters of the present invention, a deposition layer of ITOapplied to one surface of the substrate film has a function of shieldingelectromagnetic waves, and its layer thickness is preferably in therange of 50 to 600 Å, more preferably in the range of 75 to 300 Å. Thelayer thickness of less than 50 Å loses its electromagneticwaves-shielding effect, and the layer thickness above 600 Å is liable tomake cracks.

Note that the ITO layer is a kind of transparent conducting layers.Practically, the ITO layer can be obtained by depositing In2O3, whileadding SnO2 as an impurity during deposition of said In2O3. The ITOlayer has characteristics such as low specific resistance, hightransmittance or visible radiations and the like. The methods forforming the ITO layer can be divided into a chemical layer-formingmethod such as spraying method, coating method, chemical vapordeposition (OVD) method and the like, and a physical layer-formingmethod such as vacuum deposition method, sputtering method and the like.Recently, the ITO layer has been widely used particularly in liquidcrystal display devices.

Further, the flexible resin layer applied to another surface of thesubstrate film is constituted from the UV-cured product of thepolymerizing composition produced by mixing the monomeric mixturedescribed in the paragraph number [0035] with the UV-absorbing agentdescribed in the paragraph number [0040] and also thephotopolymerization initiator described in the paragraph number [0036].

In the production of the VDT filters according to the present invention,the polymerizing composition containing each of the above-describedcomponents is coated on a surface of the substrate film opposite to theITO layer winch has been deposited on one surface of the substrate film,and by irradiation of UV rays to initiate a polymerization and curingreaction of said composition, thereby producing a layer consisting ofthe UV-cured product having a high transparency and an excellentflexibility. It is preferred that the flexible resin layer is formed ata thickness of 80 μm to 1 mm, more preferably at a thickness of 125 to500μm. The thickness of the flexible resin layer of less than 80 μmexhibits a poor strength during mounting of the filters, and thethickness above 1 mm causes reduction of the adhesion property of thesubstrate film.

The thus obtained VDT filters of the present invention in which onesurface of the substrate film has a deposited ITO layer and anothersurface thereof has a flexible resin layer consisting of the UV-curedproduct can exhibit an excellent electromagnetic waves-shielding effectowing to presence of the deposited ITO layer. Further, since itsflexible resin layer can be adhered to the CRT surface by not using anadhesive, can be semi-permanently fixed, and also can be easilyseparated by hand, the filters of the present invention can berepeatedly fixed and separated in any number of times.

Further, the VDT filters of the present invention, although they do notuse an anti-static agent, can inhibit generation of electrostaticcharges, thereby preventing adhesion of trashes and dusts to the filtersand electric shock due to the generated electrostatic charges.

For the VDT filters of the present invention, an antireflective layermay be further applied over the deposited ITO layer thereof. Thematerial for forming the antireflective layer includes high-refractiveindex materials, for example, ZnO, TiO2, CeO2, Sb2O5, SnO2, ZrO2, Al2O3and the like, and low-refractive index materials, for example, MgF2,SiOx(1.50≦x≦2.00), LiF, 3NaF—AlF3, AlF3, Na3AlF6 and the like. Theantireflective layer can be formed in accordance with any optionalmethod such as vacuum deposition method, sputtering method, ion platingmethod, ion beam assisted method and the like.

In the practice of the present invention, it is preferred that athickness of the antireflective layer is so designed that a layerportion using the high-refractive index materials has a thickness of λ/2and a layer portion using the low-refractive index materials has athickness of λ/4, in which A means 550 nm.

Next, the VDT filters of the present invention will be described withreference to the accompanying drawing.

FIG. 2 is a cross-sectional view of the VDT filter illustrating onepreferred embodiment of the present invention. The illustrated VDTfilter has a deposited layer 13 of the indium-tin oxide (ITO) on onesurface of a substrate film 11 and a flexible resin layer 12 consistingof the above-described UV-cured product on another surface of thesubstrate film 11. The VDT filter further has an anti-reflective layer14 on the deposited ITO layer 13.

The high refractive index primer composition and the primer-coatedlenses using the same according to the present invention are thosecontaining the photopolymerization initiator described in the paragraphnumber [0036] in the monomeric mixture described in the paragraph number[0035]. In particular, a photocurable polymerizing composition obtainedby mixing said components in a dark room is preferred, because thecomposition can improve a shock resistance of the resulting product.

The high refractive index primer composition comprises 60 to 95% byweight of the photocurable polymerizing composition prepared asdescribed above and 5 to 40% by weight of a sol of metallic compoundhaving a high refractive index. Further, a photopolymerization initiatorin an amount of 0.005 to 10% by weight based on the total weight of thecomposition is added to the composition. More preferably, thephotopolymerization initiator is added in an amount of 0.01 to 2.0% byweight.

Further, the primer composition of the present invention can be preparedso that t contains a sol of metallic compound having a high refractiveindex, thereby removing interference fringes generated between the lenssubstrate and the hard coated layer. The sol of metallic compound havinga high refractive index is preferably a sol of organic solventdispersion type containing a compound of at least one metal selectedfrom the group consisting of Fe, Al, Ti, Zr, Sn and Sb. Moreparticularly, the metallic compound includes oxides or complex oxides ofthe metal selected from the group consisting of Fe, Al, Ti, Zr, Sn andSb, or metal oxides containing a minor amount of one of theabove-described metals. The organic solvent includes, for example,methanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve and thelike.

For the primer composition of the present invention, it is preferredthat the above-described sol of metallic compound having a highrefractive index is contained in an amount of 5 to 40% by weight, morepreferably, in an amount of 13 to 38% by weight. The content of the solof metallic compound of less than 5% by weight results in reduction ofthe refractive index, and the content above 40% by weight is liable toproduce cracks.

The ratio in incorporation of the sol of metallic compound having a highrefractive index and the polymerizing composition is preferably in therange of 1:1.5 to 1:19 with regard to the mixing ratio (weight ratio) ofthe sol and the resin, most preferably in the range of 1:2.33 to 1:9. Anexcessive increase of the sol results in liability of producing cracks,and an excessive increase of the resin results in reduction of therefractive index.

Further, other additives such as a leveling agent for improving acoatability, for improving a weathering resistance an UV-absorbingagent, an antioxidation agent and the like, may be added to the primercomposition.

In addition, the primer-coated lenses of the present invention can beproduced by coating the above-described primer composition on a surfaceof the substrate of any well-known plastic lenses, and by ultravioletirradiation. The coating method is not restrictive, and dip coating,roller coating, spray coating, flow coating, spin coating and the likecan be easily applied as the coating method. After coating of the primercomposition on the lens, UV rays may be irradiated in order to cause apolymerization and curing reaction of the polymerizing composition.Thus, a primer layer having an excellent adhesion property or fixabiltycan be formed on the substrate of the plastic lenses.

The layer thickness required for the primer layer is generally in therange of 0.01 to 2 μm, preferably in the range of 0.05 to 0.5 μm. Thethickness of less than 0.01 μm does not result in any effects as theprimer, and the thickness above 2.0 μm results in liability of producingcracks.

The obtained primer layer has a shock-absorbing property and in additionto this, it can improve an adhesion property of the hard coated layerand diminish an interference fringe generated between the lens substrateand the hard coated layer. Further, the primer layer has a hightransparency and does not damage an appearance of the resulting lens.

Any well-known hard coated layer and antireflective layer may be formedon the primer layer.

EFFECTS OF THE INVENTION

According to the present invention, it becomes possible to obtain anadhesive transparent resin, which is suitable in a coating forelectronic materials, a glass having both of the scattering-preventingfunction and the antireflective function, an adhesive agent, ashock-absorbing material, an ultraviolet-cutting sheet, anultraviolet-cutting sheet for televisions, a filter for VDTs and a highrefractive index primer composition as well as the methods for theproduction of primer-coated lenses using said primer composition, isexcellent in a coatability, adhesive property, storage stability,durability, shock resistance and the like, and is particularly excellentin a transparency and adhesion property after curing of the same.

The UV-curable composition of the present invention is excellent in acoatability, storage stability and the like, and the coated layer orcoating has both of a heat resistance and a transparency and isexcellent in an adhesion property and the like and further in electronicproperties, particularly insulating property. The coating is suitable inthe formation of surface protective and insulating coatings or layersfor various electronic materials such as a surface protective coating ofsemiconductors, an insulating layer of semiconductor-mounted devices, asurface protective coating of color filters of the liquid crystaldisplay devices, an insulating interlayer of multilayered printedcircuits, a protective coating of light guiding materials or phaseshifting materials and other coatings.

The antireflective glass with the scattering-preventing function of thepresent invention, since it simultaneously has the antireflectivefunction and the scattering-preventing function, can give a hightransmittance to the parts of display devices, construction materials,lenses, automotive parts, furniture and others, to which parts the glasshas been applied conventionally, while retaining a safety to the humanbody.

The shock-absorbing material of the present invention can be effectivelyused in the transportation or storage of fragile articles such as plateglass, glass articles, potteries and others because the shock-absorbingmaterial has excellent shock-absorbing property and flexibility. Forexample, in the transportation of plate glass, the shock-absorbingmaterial can be used in place of the conventional wood frames, and canbe sandwiched between and in close contact with each plate glass to makestacked plates of glass. Further, the shock-absorbing material has alight weight and also is not bulky, and it can be cut out by scissorsand the like into a required dimension. In the prior art methods usingthe wood frames, it is required to accept a packing volume of two timesor more higher than the volume of the plate glass, whereas when theshock-absorbing material of the present invention is alternately stackedwith the plate glass, the packing volume can be reduced to about 1.3times of the volume of the plate glass, that is, the packing volume canbe remarkably reduced in comparison with the prior art methods. Further,since an adhesive agent, nails and other means are not used in thepacking, the shock-absorbing material can be easily removed from thepacked product. Furthermore, in the production of the plate glass, ifthe shock-absorbing material of the present inversion is insertedbetween the produced plate glass and a plurality of the plate class arestored under the stacked conditions, it becomes possible to omit thework of transferring the stacked plate glass onto other packingmaterials such as wood frames for the packing purpose, remarkablyshorten the time necessary to pack the plate glass and also eliminateany troublesome matter such as careful and cautious handlings.

In addition, the shock-absorbing material of the present invention canbe produced in a simpler method and a cheaper costs in comparison withthe prior art sheets having rugged surfaces, and is useful in thestorage or transportation of glass articles or potteries, particularlydishes and the like.

The UV-cutting sheets of the present invention exhibit a hightransmittance of visible light and have a high transparency. Inaddition, since the UV-cutting sheets can effectively cut off UV rays,it becomes possible to protect the eyes and skin from harmful UV rays.Further, the UV-cutting sheets do not cause a change in color offurniture and interior articles in the room, and can prevent commercialproducts from change in color and qualities. Further, they have anexcellent flexibility, and can be directly adhered to glass windows andthe like. They can be adhered to such adherend while retaining theirsemipermanent fixation, and, if necessary, they can be easily separatedfrom the adherend by peeling off the same by hand without resulting instain or damage on the glass surface. The sheets can be cleaned withwater ishing, and can be repeatedly used many times. Further, since theydo not contain a dye, the sheets have an excellent lightfastness, andtherefore can retain their UV-cutting effect for a long period of time.

Accordingly, the UV-cutting sheets can be advantageously applied to aglass surface of a wide variety of constructions, vending machines,ocean constructions, traffic systems and the like.

The UV-cutting filters for televisions according to the presentinvention exhibit a high transmittance of visible light and have a hightransparency. In addition, since the UV-cutting filters can effectivelycut off UV rays, it becomes possible to protect the eyes from harmful UVrays. Moreover, since the filters can prevent the generation ofelectrostatic charges without using any anti-static agent, it ensures toprevent the adhesion of trashes and dusts onto the filters and alsoprevent receiving any electric shock by the electrostatic charges.Further, the filters can be produced in a very easy method, and alsothey can be easily mounted onto a surface of the televisions by directlyadhering the same to a picture area of said surface (without using anadhesive agent and the like), while retaining their semi-permanentfixation. Furthermore, the filters can be easily separated from thetelevisions by hand, and such operation of fixation and separation canbe repeatedly carried out many times without causing stain formation ordamage of the picture area of the filters. The separated filters can beeasily washed with water. Furthermore, the filters provided also withthe antireflective layer can inhibit color shading, and also they canexhibit an excellent daze-preventing effect.

The VDT filters according to the present invention exhibit a hightransmittance of visible light and have a high transparency. Inaddition, the VDT filters exhibit an excellent electromagneticwaves-shielding effect, and thus can remove any adverse influences ontothe human body and can remarkably remove a hazard to health. Further,since the VDT filters can effectively cut off UV rays, it becomespossible to protect the eyes from harmful UV rays. Moreover, since theVDT filters can prevent the generation of electrostatic charges withoutusing any anti-static agent, it ensures to prevent the adhesion oftrashes and dusts onto the filters and also prevent receiving anyelectric shock by the electrostatic charges. Further, the VDT filterscan be produced in a very easy method, and also they can be easilymounted onto a surface of the CRTs by directly adhering their flexibleresin side to said surface (without using an adhesive agent and thelike), while ensuring their semi-permanent fixation. Furthermore, theadhered VDT filters can be easily separated from the CRT surface byhand, and such operation of fixation and separation can be repeatedlycarried out many times without causing stain formation or damage of theCRT surface. The separated filters can be easily washed with water.Furthermore, the VDT filters provided also with the antireflective layercan prevent reflective projection of fluorescent lamps and lightingwindows to the CRT surface, and also they car exhibit an excellentdaze-preventing effect.

Since it is photocurable, the primer composition of the presentinvention can be cured within the curing time of several minutes.Further, it can provide lenses having a high transparency and increasedshock resistance which can diminish an interference fringe producedbetween the substrate and the hard coated layer. Moreover, use of theprimer-coated lenses of the present invention can increase an adhesionproperty of the hard coated layer.

EXAMPLES

The present invention will be further described with reference toworking examples thereof, however, the present invention should not berestricted to these examples.

Example 1

50.2 parts by weight of diallyl phthalate, 49.8 parts by weight ofpentaerythritol tetra(3-mercaptopropionate) and 0.1 parts by weight of1-hydroxycyclohexylphenylketone as a photopolymerization initiator aremixed with stirring for two hours in a dark to obtain an UV-curablecomposition. The obtained composition is spin-coated on a non-alkaliglass plate having a thickness of 1 mm, and then irradiated with UV raysfor 12 seconds at an irradiation dose of 1000 mW/cm2 to form a coatinghaving a thickness of 1.5 μm.

The obtained coating had no unevenness of coating and no defect in theappearance, exhibited a light transmittance of 98% in a visibleradiation area of 400 to 750 nm, and also showed a pencil scratchhardness of 2H. Further, the evaluation concerning adhesion to a glassplate based on a cross cut test (JIS K-5400) indicated that no peelingis observed in the coating. These characteristics are not deterioratedafter the coated glass plate is left to stand for 120 hours under theenvironmental conditions of 70° C. and relative humidity of 95%.

Next, in order to evaluate a peeling strength of the coating, an epoxyresin for sealing a liquid crystal cell is coated and hardened at athickness 10 μm on the coated glass plate. The peeling strength observedis a value of 1 kg/cm2 or more, and it is not deteriorated after theresin-coated glass plate is left to stand for 24 hours under heenvironmental conditions of 70° C. and relative humidity of 95%.Further, the similar test is repeated after the above-describedUV-curable composition is left to stand for 15 days at a roomtemperature (25° C.). No deterioration of the above characteristic isobserved.

In addition, the above procedure is repeated by using a color filtercomprising RGB picture elements formed on a transparent glass plate inaccordance with a transfer process on a laminator, in place of thenon-alkali glass plate having a thickness of 1 mm, and then coating andhardening the same UV-curable composition on the color filter inaccordance with the similar manner. The coating thus obtained shows thatthe characteristics are similar to those of the coating on thenon-alkali glass plate.

Example 2

The procedure of Example 1 is repeated to form a coating on each of thenon-alkali glass plate and color filter with the proviso that diallylisophthalate is used in place of diallyl phthalate used as one componentin the UV-curable composition. The results of evaluation test aresubstantially the same as those obtained in Example 1.

Example 3

The procedure of Example 1 is repeated to form a coating on each or thenon-alkali glass plate and color filter with the proviso that diallylterephthalate is used in place of diallyl phthalate used as onecomponent in the UV-curable composition. The results of evaluation testare substantially the same as those obtained in Example 1.

Example 4

The procedure of Example 1 is repeated to form a coating on each of thenon-alkali glass plate and color filter with the proviso that 0.1 partsby weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one is added inplace of 1-hydroxycyclohexylphenylketone used as one component,photopolymerization initiator, in the UV-curable composition. Theresults of evaluation test are substantially the same as those obtainedin Example 1.

Comparative Example 1

136 g of methyl trimethoxy silane, 198 g of phenyl trimethoxy silane and32.2 g of dianhydride of 3,3,4,4′-benzophenone tetracarboxylic acid aredissolved in 140 g of γ-butylolactone and 421 g of3-methyl-3-methoxybutanol, and 118 g of a distilled water is added withstirring at 30° C. After stirring for one hour, reflux is made at a bathtemperature of 135° C. for 2 hours to distill off alcohol and watercomponents. After the temperature of the solution is reduced to 80° C.,38.3 g of γ-aminopropyl methyldiethoxysilare, 355 g of3-methyl-3-methoxybutanol and 133 g of γ-Butylolactone are added to thesolution, and the solution is stirred for 2 hours at the sametemperature. After cooling to a room temperature, the solution isdiluted with 60 g of 3-methyl-3-methoxybutanol. The obtained solution ofsiloxane oligomer is coated on a non-alkali glass plate having athickness of 1 mm, and is dried with a hot air at 100° C. for 5 minutesto thereby obtain a cured coating. The solution is gradually gelled, andthe coating had a poor smoothness. A transparency is also poor, that is,the light transmittance is only 28% in a visible radiation area of 400to 750 nm. The pencil scratch hardness is 2B. The adhesion to a glassplate is evaluated with reference to a cross cut test (JIS K-5400) toconfirm that all the lattice patterns of the coating are peeled off fromthe glass plate. Further, the coated glass plate is left to stand for120 hours under the environmental conditions o 70° C. and relativehumidity of 95% to confirm that she lattice patterns are partiallypeeled off from the glass plate. Furthermore, the above-describedsolution of siloxane oligomer is left to stand for one week at a roomtemperature. The solution is gelled, and thus a solid product is formed.

Comparative Example 2

The procedure of Comparative Example 1 is repeated with the proviso that38.3 g of γ-aminopropyl methyldiethoxysilane is omitted in thepreparation of the solution. The obtained solution is coated or thenon-alkali glass plate as in Comparative Example 1, and the sameevaluation tests are made. The cross cut test (JIS K-5400) indicatedthat all the lattice patterns are peeled off from the glass plate.

Example 5

(1) Preparation of an Adhesive

100.4 parts by weight of diallyl phthalate, 99.6 parts by weight ofpentaerythritol tetra(3-mercaptopropionate) and 0.1 parts by weight of1-hydroxy cyclohexyl phenylkentone as a photopolymerization initiatorare mixed with stirring for 2 hours in a dark to obtain an adhesive.

(2) Production of an Antireflective Glass Having a Scattering-preventingFunction

A two-layered antireflective layer, consisting of titanium oxide at λ/2and magnesium fluoride at λ/4 (λ means 550 nm) as an antireflectivelayer, is formed on one surface of the polyethylene terephthalate filmhaving a thickness of 125 μm in accordance with the vacuum depositionmethod to obtain a plastic film having a reflecting-prevention function.Next, the adhesive prepared in the above step (1) is coated on a surfacehaving no antireflective treatment of the plastic film in accordancewith a die process, the plastic film as coated is laminated and adheredto a glass, and the laminate is irradiated with UV rays from a metalhalide lamp to thereby harden the adhesive. An antireflective glasshaving a scattering-preventing function is thus obtained.

The characteristics of the obtained glass are evaluated in accordancewith the manner described hereinafter. The results of evaluation aresummarized in the following Table 1.

1) Light Transmittance:

A light transmittance of the lass at the wavelength of 550 nm isdetermined on the spectrophorometer for UV and visible radiations.

2) Shock Resistance Test:

A steel ball of 225 g is fallen to a central portion of s the testspecimen of 30 cm×30 cm from a height of 3 m to observe an appearance ofthe damaged glass. Observation is made with regard to whether the glassis broken or bored to form a hole, whether the glass is scattered orflown into pieces, and whether the plastic film is separated from theglass.

3) Heat and Humidity Resistance Test:

An appearance of the test specimen is observed, after it is left tostand for 120 hours under the environmental conditions of thetemperature of 70° C. and the relative humidity of 95%.

Example 6

The procedure of Example 5 is repeated to obtain an antireflective glasshaving a scattering-preventing function with the proviso that in themethod of obtaining the scattering-preventing antireflective glass bycoating the previously prepared adhesive on a surface having noantireflective treatment of the polyethylene terephthalate film having areflection-preventing function in accordance with a die process,laminating and adhering the film as coated to a glass, and irradiatingthe laminate with UV rays from a metal halide lamp to thereby harden theadhesive, the polyethylene terephthalate film is laminated and adheredto both surfaces of the glass. The evaluation results for thecharacteristics of the obtained glass are summarized in the followingTable 1.

Comparative Example 3

A single surface of the glass which is the same as that used in Example5 is directly subjected to a vapor deposition treatment similar to thatof Example 5 to form an antireflective layer. The evaluation results forthe is characteristics of the obtained glass are summarized in thefollowing Table 1.

TABLE 1 test of heat Example light test of shock and humidity No.transmittance resistance resistance Ex. 5   99% no ball goes passedthrough glass Ex. 6 99.4% no ball goes passed through glass Comparative99.2% ball goes through passed Ex. 3 and scattering of glass

Example 7

100.4 parts by weight of diallyl phthalate, 99.6 parts by weight ofpentaerythritol tetra(3-mercaptopropionate) and 0.2 parts by weight of1-hydroxy cyclohexyl phenylkentone as a photopolymerization initiatorare mixed with stirring to obtain a polymerizing composition. Withregard to the adhesive obtained by using the polymerizing composition,an adhesion property, a heat resistance, a humidity resistance and anappearance are determined in accordance the following evaluation method.The evaluation results are summarized in the following Table 2.

(1) Adhesion Property

After it is coated on the polyethylene terephthalate film having athickness of 80 μm, the above-described polymerizing composition isirradiated with UV rays from an UV lamp at 80 W to make an UV-curedproduct, thereby obtaining an adhesive laminated film having an adhesivelayer (layer thickness of 25 μm) consisting of the UV-cured product. Thelaminated film is cut to obtain a test film having a width of 50 mm anda length of 200 mm. An adhesive power (N/cm) of the test film at 180°peeling is determined in accordance with the method described in theJapanese Industrial Standard, JIS-Z-0237.

(2) Heat Resistance and Humidity Resistance

After the above-described polymerizing composition is coated or a glassplate (thickness: 5 mm) so that the thickness after curing becomes 50μm, the coated composition is irradiated with UV rays from an UV lamp at80 W to form an UV-cured product, thereby obtaining an adhesivelaminated plate having an adhesive layer consisting of the UV-curedproduct.

A polarizing plate comprising a polarizing film of polyvinyl alcoholhaving a thickness of 50 μm, both sides of said film being sandwichedwith a film of cellulose triacetate having a thickness of 704 μm, islaminated to an adhesive layer-carrying surface of the adhesivelaminated plate by pressing t hem with rollers to produce aglass-laminated polarizing plate. With regard to the thus obtainedlaminated polarizing plate, a heat resistance test (left to stand at 90°C. for 120 hours) and a humidity resistance test (left to stand at 70°C. and 95% RH for 120 hours) are made, and also its spectraltransmittance (average) at 750 nm to 350 nm is determined on thespectrophotometer for UV and visible radiations, “U-4000” (produced byHitachi Co., Ltd.) to evaluate a variation thereof.

Further, the above-described procedure is repeated by using a phasedifference plate in place of the polarizing plate, and the determinationis made in accordance with the similar method. The phase differenceplate used in this determination is a phase difference plate comprisinga phase difference film of poly vinyl alcohol having a thickness of 50μm, both sides of said film being sandwiched with a film of cellulosetriacetate having a thickness of 70 μm.

Furthermore, the above-described procedure is repeated by using in placeof the polarizing plate an elliptic polarizing plate comprising acellulose triacetate film (70 μm)/a polarizing film (50 μm)/a cellulosetriacetate film (70 μm)/an adhesive film (50 μm)/a cellulose triacetatefilm (70 μm)/a phase difference film (50 μm)/a cellulose triacetate film(70 μm), and she determination is made in accordance with the similarmethod.

(3) Appearance

After the above-described durability test, an appearance of the testspecimen is visually inspected to evaluate under the following criteria:

no change is resulted - - - ∘

foaming or film separation is resulted - - - X

Example 8

The procedure of Example 7 is repeated with the proviso that diallylphthalate is replaced with diallyl isophthalate as one component of thepolymerizing composition for forming an adhesive. The evaluation resultsare summarized in the following Table 2.

Example 9

The procedure of Example 7 is repeated with the proviso that 0.2 partsby weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one is added asa photopolymerization initiator to the polymerizing composition in placeof addition of 1-hydroxy cyclohexyl phenylketone. The evaluation resultsare summarized in the following Table 2.

Example 10

The procedure of Example 7 is repeated with the proviso that diallylphthalate is replaced with diallyl terephthalate as one component of thepolymerizing composition. The evaluation results are summarized in thefollowing Table 2.

Comparative Example 4

A polymerizing composition is prepared by adding 0.1 parts by weight ofbenzoyl peroxide as a photopolymerization is initiator to 100 parts byweight of a blend of n-butyl acrylic acid acrylic acid=99:5 (weightratio), and the polymerizing composition is polymerized in toluene toobtain a solution of the acrylic copolymer. To the resulting solution ofthe acrylic copolymer, 1.0 parts by weight, based on 100 parts by weightof a solid content of the solution of the acrylic copolymer, of anisocyanate compound (trade name “Colonate L”; produced by NihonPolyurethane Co.) and 0.1 parts by weight of γ-glycidoxyropyltrimethorysilane are added, and are mixed with stirring to obtain an adhesivecomposition. The procedure of Example 7 is repeated with the provisothat the obtained adhesive composition is used in place of the adhesiveof the present invention in order to form an adhesive layer. Theevaluation results are summarized in the following Table 2.

Comparative Example 5

The procedure of Comparative Example 4 is repeated with the proviso that1.0 parts by weight of trimethoxysilane propylisocyanate is added to 100parts by weight, solid contents of the solution of the acrylic copolymerof Comparative Example 4 to obtain a composition which is used herein asan adhesive composition. The evaluation results are summarized in thefollowing Table 2.

Example 11

50.4 parts by weight of diallyl phthalate, 49.6 parts by weight ofpentaerythritol tetra(3-mercaptopropionate) and 0.1 parts by weight of2,2-dimethoxy-1,2-diphenylethane-1-one as a photopolymerizationinitiator are mixed with stirring in a dark room to obtain apolymerizing composition.

After the polymerizing composition is coated on one surface of therelease film consisting of polyvinyl chloride film having a thickness of25 μm to obtain a layer thickness of 20 μm, the above-describedpolymerizing composition is irradiated with UV rays from an UV lamp at80 W to form an adhesive layer consisting of an UV-cured product of saidcomposition. Then, a polarizing plate comprising a polarizing film ofpolyvinyl alcohol having a thickness of 50 μm, both sides of said filmbeing sandwiched with a film of cellulose triacetate having a thicknessof 70 μm, is further laminated to and over the formed adhesive layer tomake a laminated polarizing film.

Next, using a roll heating-type pressing apparatus, the above-describedlaminated polarizing film is laminated onto a transparent glass plate(thickness: 5 mm) under the application of pressing power from rollers,while peeling the release film, to obtain a glass-laminated polarizingplate. With regard to the obtained laminated polarizing plate, a heatresistance and a humidity resistance are determined in accordance withthe manner similar to that of Example 7, and also its appearance isevaluated with reference to the criteria similar to those of Example 7.

Further, the above-described evaluation procedures are repeated by usinga phase difference plate and an elliptic polarizing plate, both areidentical with those used in Example 7, in place of the polarizingplate. The results are summarized in the following Table 2.

TABLE 2 evaluation of characteristics Ex. 7 Ex. 8 adhesion property(N/cm) 1.3 1.3 heat resistance & polar. heat r. b. test 61.9 61.8humidity resistance plate a. test 60.7 60.8 (av. of spectral hum. r. b.test 61.8 61.9 trans. at 750 to 350 a. test 60.4 60.1 nm: %) phase heatr. b. test 51.8 52.0 diff. a. test 50.3 51.0 plate hum. r. b. test 51.951.9 a. test 50.0 49.8 ellip. heat r. b. test 39.1 38.8 polar. a. test36.6 37.0 plate hum. r. b. test 39.0 39.0 a. test 36.9 36.7 appearance ∘∘ Note: trans. - transmittance, polar. - polarizing, ellip. - elliptic,heat r. - heat resistance, hum. r. - humidity resistance, b. test -before test, a. test - after test. Ex. 9 Ex. 10 Comp. Ex. 4 Comp. Ex. 5Ex. 11 1.3 1.3 0.7 0.8 — 62.0 61.8 59.8 59.9 61.6 61.1 60.7 19.0 18.060.9 61.9 61.8 59.9 59.8 61.7 60.6 60.2 17.6 16.9 60.8 51.9 52.0 48.948.8 51.7 50.6 50.2 12.0 11.8 50.9 51.7 51.8 47.9 49.0 51.9 50.2 49.911.0 10.5 50.2 39.0 39.0 30.0 30.3 39.1 36.8 36.9 5.5 3.9 37.8 38.8 38.931.0 30.7 38.8 37.1 36.8 3.1 2.8 37.0 ∘ ∘ x x ∘

Example 12

A polymerizing composition which is prepared by mixing 100.4 parts byweight of diallyl isophthalate, 99.6 parts by weight of pentaerythritoltetra(3-mercaptopropionate), 0.2 parts by weight of a mixture of2-hydroxy-2-methyl-1-phenylpropane-1-one and bisacylphosphine oxide(produced by Ciba-Geigy (Japan) Ltd.; trade name “CGI-1700”) as aphotopolymerization initiator, and 0.6 parts by weight of2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol](produced by Kyodo Yakuhin Kabushikikaisha; trade name “Biosorb 583”) asa stabilizer in a dark is coated on a polyethylene terephthalate filmhaving a thickness of 125 μm, and the coated polymerizing composition isimmediately irradiated with UV rays from a metal halide lamp to form aflexible resin layer having a layer thickness of 0.1 mm. The UV4irradiation time is 300 seconds, and an output of the lamp is 120 W.

The thus obtained sheet had a high shock-absorbing power, along with anexcellent flexibility. The shock resistance is determined in accordancewith the following method.

A test sample is prepared by adhering the sheet to both surfaces of theglass plate having a thickness of 1.2 mm, and a steel ball of 16 g isfallen to the test sample from a height of 127 cm. No breakage andscattering of the glass is observed.

Example 13

The procedure of Example 12 is repeated to obtain a sheet with theproviso that diallyl isophthalate is replaced with diallylterephthalate. The shock resistance test is made in accordance with themethod described in Example 12. No breakage and scattering of the glassis observed.

Example 14

The procedure of Example 12 is repeated to obtain a shock-absorbingmaterial with the proviso that diallyl isophthalate is replaced with shesame amount of diallyl phthalate, and 2 parts by weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one and 0.01parts by weight of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butane-1-one are addedas a photopolymerization initiator. The shock resistance test is made inaccordance with the method described in Example 12. No breakage andscattering of the glass is observed.

Example 15

100.4 parts by weight of diallyl isophthalate, 99.6 parts by weight ofpentaerythritol tetra(3-mercaptopropionate), 0.2 parts by weight of amixture of 2-hydroxy-2-methyl-1-phenylpropane-1-one and bisacylphosphineoxide (produced by Ciba-Geigy (Japan) Ltd.; trade name “CGI-1700”) as aphotopolymerization initiator, and 0.6 parts by weight of2,2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol](produced by Kyodo Yakuhin Kabushikikaisha; trade name “Biosorb 583”) asan UV-absorbing agent are mixed in a dark. The obtained polymerizingcomposition, while it is molded in accordance with a die process toobtain a sheet-like product, is irradiated with UV rays from a metalhalide lamp to obtain a sheet having a thickness of 0.15 mm. The UVirradiation time is 300 seconds, and an output of the lamp is 120 W.

The obtained sheet had a high transparency. Further, since it has anexcellent flexibility, the sheet could be directly adhered to the glasswindows and the like of the constructions, and its adhesion could besemi-permanently maintained. Furthermore, the adhered sheet can beeasily peeled off from the glass surface by hand, without causing stainformation and damages in said surface.

With regard to the obtained sheet, its transmittance of visibleradiations and its effect of cutting or cutting a rays are determined inaccordance with the manner described hereinafter. The results aresummarized in the following Table 3.

1) Transmittance of Visible Radiations:

A transmittance of the sheet at the wavelength of 550 nm is determinedon the spectrophotometer for UV and visible radiations.

2) Transmittance of UV Rays:

A transmittance of the sheet at the wavelength of 300 nm is determinedon the spectrophotometer for UV and visible radiations. The UV cuttingeffect could be appreciated from the results.

Example 16

A two-layered antireflective layer consisting of TiO2 λ/2) and MgF2(λ/4) (A means 550 nm) as an antireflective layer is formed on onesurface of the UV-cured product obtained in Example 15 accordance withthe vacuum deposition method.

The obtained sheet had a transmittance of visible radiations of 90%(average of 350 to 750 nm) The UV cutting effect is determined in themanner similar to that of Example 15, and the results are summarize, inthe following Table 3.

Example 17

The procedure of Example 15 is repeated to obtain an UV-cutting sheetwith the proviso that diallyl isophthalate is replaced with diallylterephthalate. The results of evaluation are summarized in the followingTable 3.

Example 18

The procedure of Example 15 is repeated to obtain an UV-cutting sheetwith the proviso that diallyl isophthalate is replaced with the sameamount of diallyl phthalate, and 2 parts by weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one and 0.01parts by weight of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butane-1-one are addedas a photopolymerization initiator. The results of evaluation aresummarized in the following Table 3.

TABLE 3 transmittance Example of visible transmittance No. radiations ofUV rays 15 90% 0% 16 98% 0% 17 90% 0% 18 91% 0%

Example 19

100.4 parts by weight of diallyl isophthalate, 99.6 parts by weight ofpentaerythritol tetra (3-mercaptopropionate), 0.2 parts by weight of amixture of 2-hydroxy-2-methyl-1-phenylpropane-1-one and bisacylphosphineoxide (produced by Ciba-Geigy (Japan) Ltd.; trade name “CGI-1700”) as aphotopolymerization initiator, and 0.6 parts by weight of2,2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol](produced by Kyodo Yakuhin Kabushikikaisha; trade name “Biosorb 583”) asan UV-absorbing agent are mixed in a dark. The obtained polymerizingcomposition, while it is molded in accordance with a roil coater processto obtain a sheet-like product, is irradiated with UV rays from a metalhalide lamp to obtain a sheet having a thickness of 0.2 mm. The UVirradiation time is 300 seconds, and an output of the lamp is 120 W. Thethus obtained UV-cured product is then cut in conformity with the sizeof the image-displaying surface of the television to obtain a filter.

The filter had a high transparency. Further, since it has an excellentflexibility, the filter could be directly adhered to theimage-displaying surface of the television, and its adhesion can besemi-permanently maintained. Furthermore, the adhered filter could beeasily peeled off from the image-displaying surface by hand, withoutcausing stain formation and damages in said surface.

With regard to the obtained filter, its transmittance of visibleradiations, transmittance of UV rays (UV-cutting off effect) and effectsof inhibiting generation of electrostatic charges are determined inaccordance with the manners described hereinafter, respectively. Theresults are summarized in the following Table 4.

1) Transmittance of Visible Radiations:

A transmittance of the filter at the wavelength of 550 nm is determinedon the spectrophotometer for UV and visible radiations.

2) Transmittance of UV Rays:

A transmittance of the filter at the wavelength of 300 nm is determinedon the spectrophotometer for UV and visible radiations.

3) Effects of Inhibiting Generation of Electrostatic Charges:

A dielectric constant of the filter is determined in accordance with themethod described in the Japanese Industrial Standard, JIS K6911.

By the vacuum deposition method, a two-layer antireflective layerconsisting of TiO2 at λ/2 as an antireflective layer, and MgF2 at λ/4 (λmeans 550 nm) formed on the TiO2 layer, is formed on one of surfaces ofthe UV-cured product obtained in Example 19.

With regard to the obtained filter, its transmittance of visibleradiations, UV-cutting off effect and effects of inhibiting generationof electrostatic charges are determined in the above-described manner,and the results are summarized in the following Table 4.

Example 21

The procedure of Example 19 is repeated to obtain a TV filter with theproviso that diallyl isophthalate is replaced with diallylterephthalate. The results of evaluation are summarized in the followingTable 4.

Example 22

The procedure of Example 19 is repeated to obtain a TV filter with theproviso that diallyl isophthalate is replaced with the same amount ofdiallyl phthalate, and 2 parts by weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one and 0.01parts by weight of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butane-1-one are addedas a photopolymerization initiator. The results of evaluation aresummarized in the following Table 4.

TABLE 4 transmittance inhibition Example of visible transmittance ofstatic No. radiations of UV rays charges* 19 91% 0% 2.2 20 99% 0% 2.1 2191% 0% 2.2 22 91% 0% 2.2 *Effects of inhibiting generation ofelectrostatic charges: dielectric constant at 1 MHz.

Example 23

A surface of 100-μm thick polyethylene terephthalate film having avacuum-deposited ITO layer of the layer thickness of 150 Å, the surfacebeing opposed to said ITO layer, is coated with a polymerizingcomposition which is prepared by mixing 100.4 parts by weight of diallylisophthalate, 99.6 parts by/weight of pentaerythritoltetra(3-mercaptopropionate), 0.2 parts by weight of a mixture of2-hydroxy-2-methyl-1-phenylpropane-1-one and bisacylphosphine oxide(produced by Ciba-Geigy (Japan) Ltd.; trade name “CGI-1700”) as aphotopolymerization initiator, and 0.6 parts by weight of2,2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol](produced by Kyodo Yakuhin Kabushikikaisha; trade name “Biosorb 583”) asan UV-absorbing agent are mixed in a dark room. Immediately aftercoating, the coated polymerizing composition is irradiated with UV raysfrom a metal halide lamp to obtain a flexible resin layer having a layerthickness of 250 μm. The UV irradiation time is 300 seconds, and anoutput of the lamp is 120 W.

The thus obtained VDT filter had a high transparency and since it had anexcellent flexibility, a flexible resin layer side of the filter couldbe directly adhered to a CRT surface of the VDTs and its adhesion couldbe semi-permanently maintained. Further, the adhered filter could beeasily peeled off from the CRT surface by hand, without causing stainformation and damages in said surface.

With regard to the obtained filter, its transmittance of visibleradiations, transmittance of UV rays and effects of inhibitinggeneration of electrostatic charges are determined in accordance withthe manners described hereinafter, respectively, and the results aresummarized in the following Table 5. Further, electromagneticwaves-shielding effects determined in accordance with the followingmethod are plotted in FIG. 3.

1) Transmittance of Visible Radiations:

A transmittance of the filter at the wavelength of 550 nm is determinedon the spectrophotometer for UV and visible radiations.

2) Transmittance of UV Rays:

A transmittance of the filter at the wavelength of 300 nm is determinedon the spectrophotometer for UV and visible radiations. The UV cuttingeffect could be appreciated from the results.

3) Effects of Inhibiting Generation of Electrostatic Charges:

A dielectric constant of the filter is determined in accordance with themethod described in the Japanese Industrial Standard, JIS K6911.

4) Electromagnetic Waves-shielding Effects:

Electromagnetic waves-shielding effects of the filter is determined inaccordance with the Advantest method.

Example 24

A two-layered antireflective layer consisting of TiO2 (λ/2) and MgF2(λ/4) (λ means 550 nm) as an antireflective layer is formed on avacuum-deposited ITO layer of the filter obtained in Example 23 inaccordance with the vacuum deposition method.

With regard to the obtained Alter, its transmittance of visibleradiations, transmittance of UV rays and effects of inhibitinggeneration of electrostatic charges are determined in theabove-described manner, and the results are summarized in the followingTable 5. The electromagnetic waves-shielding effects are plotted in FIG.4.

Example 25

The procedure of Example 23 is repeated to obtain a VDT filter with theproviso that diallyl isophthalate is replaced with diallylterephthalate. The results of evaluation are summarized in the followingTable 5 and FIG. 5.

Example 26

The procedure of Example 23 is repeated to obtain a VDT filter with theproviso that diallyl isophthalate is replaced with the same amount ofdiallyl phthalate, and 2 parts by weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one and 0.01parts by weight of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butane-1-one are addedas a photopolymerization initiator. The results or evaluation aresummarized in the following Table 5 and FIG. 6.

TABLE 5 transmittance inhibition Example of visible transmittance ofstatic No. radiations of UV rays charges* 23 90% 0% 2.1 24 98% 0% 2.0 2590% 0% 2.1 26 90% 0% 2.1 *Effects of inhibiting generation ofelectrostatic charges: dielectric constant at 1 MHz.

Example 27

(1) Preparation of a Primer Composition

13.3 parts by weight of a titanium oxide-zirconium oxide composite solof methanol dispersion type (solid content of 20% by weight; produced byShokubai Kasei Kogyo Kabushikikaisha; trade name “Optolake 1120Z”), 40.6parts by weight or diallyl isophthalate, 39.94 parts by weight ofpentaerythritol tetra(3-mercaptopropionate) 0.8 parts by weight of amixture of 2-hydroxy-2-methyl-1-phenylpropane-1-one and bisacylphosphineoxide (produced by Ciba-Geigy (Japan) Ltd.; trade name “CGI-1700”) as aphotopolymerization initiator, and 0.7 parts by weight of a siliconesurfactant, L-7001 (trade name; produced by Nihon Unicar) as a levelingagent are stirred in a dark to obtain an uniform primer composition.Attention is made so that the primer composition is not exposed tolights.

(2) Coating

After an urethane-based plastic lens having a refractive index (n) of1.6 is cleaned, the lens is coated with the primer composition preparedin the above step (1) in accordance with a spin coating method. In thisspin coating process, the revolution speed is 5000 rpm, and therevolution time is 30 seconds. Immediately after coating, the coatedprimer composition is irradiated with UV rays from a metal halide lampat an output of 120 W for 300 seconds to thereby cause UV curing andform a primer layer having a layer thickness of 0.1 μm.

Next, a hard coated layer (refractive index of 1.62) having a layerthickness of 2.0 μm is formed on the produced primer layer in accordancewith a dip coating method. The hard coating solution used is a highrefractive index hard coating solution produced by Shokubai Kasei KogyoKabushikikaisha (trade name “PSI-118”). The pulling speed is 100 mm/minand the curing conditions are 2 hours at 110° C. Further, anantireflective multicoating is applied over the hard coated layer byvacuum depositing four thin layers of, from a lens side to an atmosphereside, a mixture of ZrO2 and SiO2 wherein a mixing ratio of ZrO2 and SiO2based on the weight ratio is 1:1, ZrO2, Ta2O5 and SiO2. Each thin layerhad an optical layer thickness of λ0/4, λ0/4, λ0/4 and λ0/4 (λ0 is 550nm) in the described order. The thus obtained lens did not show anyproblem in its appearance. The lens had a transmittance of 99%.

(3) Evaluation

A shock resistance of the lens is determined by conducting a fallingball test in accordance with the guideline described in FDA Standards inwhich a steel ball having a weigh of 16 g is fallen to the lens from aheight of 127 cm, followed by observing the lens. In the falling balltest, the lens having a prime layer produced by using the primercomposition of the present invention did not cause any problem.

Comparative Example 6

A lens substrate is dipped in a commercially available primer forpolycarbonate (produced by Shinetsu Kagaku Kabushikikaisha; trade name“Primer PC”), and then Dulled at 100 mm/min, followed by curing at 50°C. for one hour. The layer thickness of the obtained primer layer is 0.6μm. The lens is produced in accordance with the manner similar to thatof Example 27 except for the above-described primer coating, andsubjected to the falling ball test. A back surface of the lens iscracked.

The procedure of Example 27 is repeated to prepare a primer compositionand produce a primer coated lens with the proviso that in the step (1)diallyl isophthalate is replaced with diallyl terephthalate. Theobtained lens did not cause any problem in the falling ball test.

What is claimed is:
 1. In combination, at least one fragile article anda shock-absorbing material, said shock absorbing material comprising aphotocured product of polymerizing composition in a form of a sheetwhich comprises a monomeric mixture of at least one of diallylphthalate, diallyl isophthalate and diallyl terephthalate, andpentaerythritol tetra(3-mercaptopropionate) in an equivalent ratio of2:1 to 1:3; and a photopolymerization initiator of 0.005 to 10% byweight being added to said polymerizing composition.
 2. Anultraviolet-cutting sheet, comprising a photocured product ofpolymerizing composition which comprises a monomeric mixture of at leastone of diallyl phthalate, diallyl isophthalate and diallylterephthalate, and pentaerythritol tetra(3-mercaptopropionate) in anequivalent ratio of 2:1 to 1:3; and a photopolymerization initiator of0.005 to 10% by weight being added to said monomeric mixture, said sheethaving opposing surfaces, and either of said opposing surfaces beingcapable of being applied to a surface.
 3. The ultraviolet-cutting sheetaccording to claim 2, wherein an antireflective layer is provided on onesurface of said photocured product.
 4. An ultraviolet-cutting sheet fortelevisions comprising a photocured product of polymerizing compositionwhich comprises a monomeric mixture of at least one of diallylphthalate, diallyl isophthalate and diallyl terephthalate, andpentaerythritol tetra(3-mercaptopropionate) in an equivalent ratio of2:1 to 1:3; and a photopolymerization initiator of 0.005 to 10% byweight being added to said polymerizing composition, said photocuredproduct being in a form of a sheet having opposing surfaces, and eitherof said opposing surfaces being capable of being applied to a surface.5. The ultraviolet-cutting sheet for televisions according to claim 4,wherein an antireflective layer is provided on one surface of saidphotocured product.
 6. The combination according to claim 1, whereinsaid at least one fragile article comprises plate glass.
 7. Thecombination according to claim 1, wherein said shock absorbing materialis sandwiched between plate glass.
 8. The combination according to claim1, wherein said at least one fragile article comprises a glass article.9. The combination according to claim 1, wherein said at least onefragile article comprises pottery.
 10. In combination, the ultra-violetcutting sheet of claim 4 and a television display.